Diamino phosphorus derivatives of ring nitrogen heterocyclic compounds



United States Patent 3,150,149 DIAMING PHOSPHORUS DERIVATIVES 0F RINGNITROGEN HETERQCYCLIC CQMPQUNDS Jan Hendrik Uhienhroek and BernardusGerhardus van den Bos, Weesp, Netherlands, assignors to North AmericanPhilips Company, Inc., New York, N.Y., a corporation of Delaware NoDrawing. Filed Mar. 7, 1960, Ser. No. 12,952 Claims priority,application Netherlands Mar. 6, 1959 6 Claims. (Cl. 260-310) Thisinvention relates to new and novel phosphorus containing heterocycliccompounds, to methods of preparing these compounds and to the use ofthese compounds as pesticides.

As the population of the world steadily increases the demand for foodalso increases. One of the most important means of meeting this everincreasing demand for food is to increase the crop production of landunder cultivation. In order to obtain the maximum crop yield it isnecessary to prevent plant destructive pests such as vide new chemicalcompounds that are useful for the destruction of plant harmful pests andwhich are relatively harmless to warm blooded animals.

These and other objects of the invention will be apparent from thedescription that follows:

According to the invention new and novel phosphorus containingheterocyclic compounds are provided. These compounds correspond to thegeneral formula:

wherein Q represents a heterocyclic ring containing radical in which theheterocyclic ring contains from 2 to 4 hetero atoms at least one ofwhich is nitrogen and has aromatic properties, X and X represent amember of the group consisting of oxygen and sulfur, R R R and R eachrepresent lower alkyl radicals and X is bound to a carbon atom of theheterocyclic ring. In these compounds it is preferred that the heteroatoms in the heterocyclic ring be selected from the group consisting ofN, O and S.

The heterocyclic ring may be fused with a benzene ring and also may besubstituted by one or more substituents. Among these substituents arealkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, aralkyl, alkylamino,dialkylamino, arylamino, diarylamino, acylamino, alkoxy, alkyl mercapto,halogen atoms, particularly chlorine atoms and amino groups. Of thesesubstituents amino, phenyl and alkyl groups containing from 1 to 7carbon atoms are preferred. Examples of radicals that Q may representthus are benzoxazolyl, 1,2,4striazolyl, S-phenyl-1,2,4-triazolyl,S-pentyl-1,2,4-triazoly1, 5-methyl-1,2,4-triazolyl, S-chloro-1,2,4-triazo'lyl, S-heptyl-1,2,4-triazolyl, 1,2,4-triazolyl, 4-phenyi-l,2,3-triazolyl, 4-methyl-1,2,3-triazolyl, tetrazolyl,3-methyl-1,2,4-triazolyl, oxazolyl, thiazolyl, 4-methylthiazolyl, 4phenyl thiazolyl, 4 (4' bromophenyl)thiazolyl, benzothiazolyl,imidazolyl, 4-chloro-imidazolyl, 2- isopropyl-4-methyl-pyrimidyl,4,6-dimethyl pyrimidyl, 2, 4-dimethyl-pyrimidyl, imidazolyl, indazolyl,pyridazolyl, pyrazinyl, 3-amino-l-phenyl-pyrazolyl,l-phenyl-B-methyl-pyrazolyl, 3-methyl-pyrazolyl, 1 (4 nitrophenyl)-3-methyl-pyrazolyl, 3-methyl-pyrazolyl,l-(4'-chlorophenyl)-3-methylpyrazolyl, 1,3-dimethyl-pyrazolyl, l-nonyl-3-methyl-pyrazolyl, 1,3-diphenyl-pyrazolyl,1-(2'-ch1orophenyl)-3-methy1-pyrazolyl, Z-phenyl-pyrazolyl,l-pentyl-3-methyl-pyrazolyl and 1-pentyl-3-phenyl-pyrazolyl.

R R R and R preferably represent alkyl groups containing from 1 to 5carbon atoms. Of these, methyl is the most suitable.

These novel compounds are very effective insecticides,

fungicides and acaracides and are particularly useful in are relativelynon-toxic to Warm-blooded animals.

Of the novel compounds of the invention it has been found that thederivatives of pyrazole-S-one particularly those substituted on theheterocyclic ring by alkyl groups containing 1 to 9 and preferably 1 to4 carbon atoms and those substituted with phenyl preferably chlorophenylgroups have excellent insecticidal and fungicidal properties. In factsome of these derivatives, particularly those in which thepyrazole-S-one is substituted on the ring nitrogen by an alkyl or phenylgroup, have been found to be the most effective fungicides tested.

The preparation of the compounds according to the. invention may becarried out so that the amidophosphoryl or the amidothionophosphorylgroup is carried out in 1 or 2 reaction stages.

In these methods a heterocyclic compound QX H .or Q-X -Me wherein X, andQ have their above-noted meanings and Me represents a metal preferablesodium or potassium is reacted with a compound corresponding to thegeneral formula selected from the group consisting of halogen,particularly chlorine,

R3 and N wherein R R R and R have their previously indicated meaning toproduce a compound corresponding to the general formula either directlyor when Y or Y represents a halogen after treatment with a dialkylamine.

In those cases in which n=0 the products are oxidized or reacted withsulfur to produce compounds in which 11:1. In any event when a compoundQX -H is employed or when Y or Y represents a halogen the reaction iscarried out in the presence of a hydrogen-halide binding agent such asamines, particularly trialkylamines for example trimethylamine,triethylarnine, N,N-dialkylanilines, pyridine and particularlyhomologues there of for example picolines, lutidines and collidine andmixtures thereof.

Another group of hydrogen-halide binding agents which may be employedcomprises compounds of sodium,

erably carried out in the presence of a solvent for the heterocycliccompounds used as starting material. able solvents are, for example,aliphatic and aromatic hydrocarbons, such as petroleum ether andbenzene, aliphatic ethers, tertiary amines, for example pyridines,nitriles such as acetonitrile, ketones such as acetone andmethylethylketone, esters such as ethyl acetate, and in ad- When dition,nitrobenzene and carbon tetrachloride. metal compounds of the formula QXMe are employed, these solvents may also be used as diluting agents.

The reactions are preferably carried out at elevated temperature, forexample between C. and 120 C.

EXAMPLE I 10.2 g. of the sodium derivative of benzoxazolone (obtained byevaporating equivalent quantities of sodium ethylate in ethanol andbenzoxabolone until no more ethanol distilled), 80 cc. of acetonitrileand 14.2 g. of bis (N.N dimethylamido) phosphorylchloride were mixed andrefluxed. After cooling, the separated sodium chloride was sucked oifand the filtrate evaporated. The residue was dissolved in ether, theethereal solution was washed with water, dried on sodium sulphate andevaporated. The residue is a pale yellow oil. Yield: 15.6 g. (78

P=11.50% calculated. P=11.0% found.

EXAMPLE XXVI 17.0 g. of 3-hydr.oxy 1,2,4-triazole were suspended in amixture of 40 cc. of collidine and 10 cc. of acetonitrile. 34.1 g. ofhis (dimethylamido)-phosphorylchloride were added dropwise at atemperature between 70 C. and 80 C. At this temperature, the reactionmixture was then stirred for about 3 hours. After cooling, the resultingprecipitate was sucked off, dissolved in water, and neutralized withsodium hydroxide solution. The collidine reformed on netralization wasremoved by washing with petroleum ether (boiling range 40 C. to C.). Theaqueous solution was evaporated and the residue extracted with methanol.The methanolic solution was evaporated and the residue crystallized froma mixture of chloroform and ethylacetate (1:1).

Yield: 16 gms. (37%). Melting point: 147149.5 C.

The Examples II to XXV, given in Table I have been carried out in amanner analogous to that of Example I, and Example XXVII in a manneranalogous to that of Example XXVI. In this table there are successivelystated the numbers of the example, the starting materials, the dilutingagents, the reaction temperatures, the yields of resulting products,calculated on the quantities of heterocyclic compound used and theboiling point or melting point of the resultant product. The boilingpoint is indicated by F, followed by the temperature in C. and therelative pressure in mm. mercury column and the melting point isindicated by S and expressed in C.

In Table II, the name of the resulting compound is given next to thenumber of the example.

Table I No. Starting substances Diluting agent Reaction- Yield inPhysical constants temp., 0. percent Benzoxazolone. Acetrmitrila About80..-- 78 Benzoxazolethione d :75 S=109111 O. 3-mercapto-triazole-l,2,4Acetone Ab out 55.-.. 50 S 185187 C 3-mercapto-fi-pentyl-triazole-l,2,4dn (011. 2-hydroxy-4-rnethylthiazole-l,3 Acetonitrile 86 F 1l9119.5 O.at 0.2-0.3 mm. 2-hydroxy-4-phenylthiazole-l,3. do-.. 86 S= C2-hydr0xy-4(4-bromophenyl)-th do 67 S 6162 O2-is0propy1-4-methyl'6-hydroxypyrimidine Benzene. do 81 (011 o4,6-dimethyl-2-hydroxypyrimi dine Ab out 140-. 47 S 60-75 C2,4-dimethyl-fi-hydroxypyrirnidine About 80.- 683-pheny1-5-mercapto-thiadiazole-l,2,4 Aeetonitnle do 73 0.S-amino-l-phenylpyrazole-fi-oue .do -80 33 S 142143 C-phenyl-S-methylpyrazole-5-one Benzene. About 60.- 703-methy1pyrazole-5-one Acetnmtrile do 60 Do. 01-(4-nitr0phenyl)-3-methy1-pyrazole-5-one B enzene About 70 55 S 118-119C 1-(4-ch1or0phenyl)-3-methyl-pyrazo1e-5-one Aeetonitrile. About 65..-.67 S 8485 C ,3-dimethylpyrazole-5-one 1 Ab out 96 (011.) Indazolone 99Do. 1-nony1-3-niethylpyrazole-5-one Do. 1,3-di henylpyrazole-5-one. 95}Do. 0 1-(2-c ilorophenyl) -3-methy1pyrazole-5-one 80 S 93-943-phenylpyrazole-5-one 84 S= 229231 C.

1-pentyl-3methylpyrazole-5-0ne 87 (01].)

1-penty1-3-phenylpyraz0le-5-0n 99 Do Be'mthiamlnne 77 Do. 3-hydroxytriazole-1,2,4 70-80 S l47149.5 C 3-luethyl-5-hydroxy triazole-1,2,4 cin 84 (01L) Table 11 ProductBis(N,N-dimethylamido)benzoxazolyl-Z-phosphate.Bis(N,N-dimethylamido)-S-benzoxazolylphosphato.Bis(N,N-dimethylamido)-S-(triazo1yl-l,2,4)-3-phosphate.Bis(N,N-dimethylamido)-S-(5-peutyltriazolyl-l,2,4)-3- phosphate.Bisl(Nt,N- 'methylamido)-O-(4-methylthiazolyl-2)phosp e. Bis1(1N,N-dimethylarm'do) -O- (4-phenylth iazolyl-2) ph osateBis(N,N-dlrnethylamido) O-(l)-4-nitropheny1(3-methylpyrazolyl-5)phosphate.

Bis (N,N-dimethylamido) -O (1) 4-chl0r0phenyl(3-methylpyrazolyl-5)phosphate.

Bis(N,N-dimethylamido)-O-(1,3-cli1nethylpyrazolyl-5) phosphate.

Bis(N,N-dimethylamido)-O-indazo1ylphosphate.

Bis (N ,N-dimethylami do) -O-(I-nonyLB-methylpyrazolyl-5) phosphate.

XX BislgNdi-dimethylamidm-O-(1,3-diphenylpyrazolyl-5) p osp ate.

XXI Bis(N,N-dimethylamido)-O-[1-(2-ehlorophenyl)-3-methylpyrazolyflphosphate.

XXII BisN,N-dimethylamido)-O-(3-phenylpyrazolyl-5)phosp ate.

XXIV..-" Eis)(I 1I ,N-(1limethylamid0)-O-(l pentyl-3-phenylpyraz0lyl- 5p 105]) iate.

XXV Bis(N,Ndimethylamido)-O benzthiazolyl-2-phosphate.

XXVI Bis(N,N-dimethylamido)-O-(triazoly1-1,2,4)-3-phosphate.

XXVII Bis(N ,N-dimethylarnido)-O-(3-n1ethy1triazolyl-1,2,4)-5-phosphate.

The active compounds of the invention may be formulated and employed inthe conventional manner for destroying the noxious organisms. Thus theymay be mixed with solid carriers, ground to the desired particle sizeand dusted on the crops. Examples of the solid carriers that may beemployed are pipe clay, diatomaceous earth, kaolin, dolomite, talcum,gypsum, bentonite, attapulgite, kieselguhr, celite, wood meal, tobaccodust, ground walnut shells and ground cocoanut shells. In these duststhe concentration of the active compound usually lies between about 122%by weight.

The active compounds of the invention may also be applied to the cropsin the form of suspensions in a volatile liquid, usually water. Inpreparing such a suspension the active compound is formed into awettable powder and then dispersed in a volatile solvent such as water.In the formulation of the wettable powder the active compound is groundwith a solid carrier of the type employed in forming a dust and asuitable dispersion agent such as a lignin sulfonate or a naphthalenesulfonate and/or a suitable wetting agent such as a fatty acidsulfonate, an alkaryl sulfonate or an acid condensation product of thetype sold under the trademark Igepon are added. In the wettable powderthe concentration of the active compound may vary between wide limits.However, a concentration of between about to 80% by weight is usuallypreferred.

Finally the active compounds of the invention may be applied to thecrops in the form of emulsions in water or other volatile liquids. Inpreparing these emulsions the active compound is first formed into amiscible oil. These miscible oils contain besides the active compound awater insoluble solvent for the active compound and an emulsifier. Amongsolvents that may be employed are xylene, toluene, dioxane, aromaticpetroleum distillates such as solvent naptha, distilled tar oil,tetralene and cyclohexane and mixtures of these liquids. Among theemulsifiers that may be employed are the alkyl phenoxy-glycol ethers,polyoxyethylene sorbitan esters of fatty acids,polyoxyethylene-sorbitolesters of fatty acids and the emulsifiers knownby the trademarks Tween, Triton and Atlox. The concentration of theactive-compound in the solvent is usually about 250% by weight and inthe emulsion the concentration of the active compound is usually betweenabout 0.01 to 0.5% by weight.

While we have described our invention in connection with specificembodiments and applications, other modifications thereof will bereadily apparent to those skilled in this art without departing from thespirit and scope of the invention as defined in the appended claims.

What is claimed is:

1. A phosphorous heterocyclic compound of the formula:

wherein Q is a monovlaent heterocyclic ring containing radical selectedfrom the group consisting of the unsubstituted heterocyclic radicals:benzoxazolyl, 1,2,4- triazolyl, thiazolyl, pyrimidyl, pyrazolyl,1,2,4-thiodiazolyl and indazolyl and said heterocyclic radicalssubstituted with alkyl of 1 to 7 carbon atoms, phenyl, chlorophenyl,bromophenyl, nitrophenyl, amino and chloro and X and X are bivalentatoms of group VI of the periodic table having atomic weights of 16 to32 inclusive and Q is joined to X through a carbon atom in theheterocyclic ring.

2. The compound of claim 1 in which Q is pyrazole- S-one substitutedwith alkyl of 1 to 4 carbon atoms at one of the ring nitrogen atoms.

3. The compound of claim 1 in which Q is pyrazole- 5-one substitutedwith the phenyl at one of the ring nitrogen atoms.

4. The compound of claim 1 in which Q is pyrazole- 5-one substitutedwith the chlorophenyl at one of the ing nitrogen atoms.

5. The compound of claim 1 in which Q is pyrazole- S-one substitutedwith the nitrophenyl at one of the ring nitrogen atoms.

6. The compound of claim 1 in which Q is pyrazole- 5-one substitutedwith the pentyl at one of the ring nitrogen atoms.

References Cited in the file of this patent UNITED STATES PATENTS2,552,537 Drake et al May 15, 1951 2,751,384 Coover et a1 June 19, 19562,844,510 Lorenz et al. July 22, 1958 2,888,379 Bruning et al May 26,1959 3,010,969 Rigterink Nov. 28, 1961 FOREIGN PATENTS 713,278 GreatBritain Aug. 11, 1954 246,915 Switzerland Feb. 15, 1947 OTHER REFERENCESFrear et al., J. of Economic Entomology, vol. 40, pages 736-741 (1947).

1. A PHOSPHOROUS HETEROCYCLIC COMPOUND OF THE FORMULA:
 2. THE COMPOUNDOF CLAIM 1 IN WHICH Q IS PYRAZOLE5-ONE SUBSTITUTED WITH ALKYL OF 1 TO 4CARBON ATOMS AT ONE OF THE RING NITROGEN ATOMS.